Manufacture of catalysts



NGV.' 25,- 1945'- K.. D. ASHLEY; AL

MNUFACTURE OF ('TU'JYSTS Filed sept. 22, A1942 \Q NJ@ Patentedy Nov. 26, 1946 v 2,411,320l I if e MANUFAcTUnE oF cA'rALY's'rs 'Kenneth D. Ashley, Noroton, a nd Alphons v0.

Jaeger, Greenwich, Conn., assgnorsto' American 'Cyanam'id Company, New York, N. Y., a Corporation-@Maine 'Y .i 'e .t x

applicati@ september 221942', serial No; `459,262

' 201mm.l (c1.252'250`) f y catalysts in the quantities commensurate with UNITED This invention relates 'to the manufacture of f catalysts, and more particularly tothe manufacthe extent of the-petroleumiridi1stry.'1;

ture of gel-type catalysts containing oxides or hydrous oxides of'metals of .the third and fourth v groups of the periodic system. While the princi# ples of the invention may be applied tothe prot duction of gel-type catalysts for any purpose, they are particularly useful in themanufacture of cracking catalysts, dehydration catalysts and dehydrogenation catalysts of any desired particle size, such as those employed for the catalytic dehydrogenation or cracking of petroleum fracn lystsare produced by precipitating solutions containing aluminum or mixtures of 'alumina' with zirconium or titanium on a precipitated silica hydrogel. Representative catalysts of the first class are described in U. S. Patents Nos. 2,285,314 and 2,287,917. It is a principal object ofthe present f invention to provide -an improved-methodfor the manufacture of catalysts of these classes,which manufacture ofv gel-type catalysts of'high efliciency. In their broader aspects, however, some of the features of the present invention are applicable to the `manufacture of any gel-'type catalyst consisting'of cr comprising active silica.'

Gel-type catalysts containing .active vsilica should be substantially free from alkaliv metal compounds and other Water-soluble salts that might act as a flux in the iinishedcatalyst composition. Such catalysts should also be of'relatively uniforml particle size, with a minimum ticularly directed to methods forthe preparation of gel-type catalysts containing `active silica,

" salts `have been* removed jirfo'rnthe freshly precipl- Ordinary silica gel is` preciuitated by acdifylng 'relatively strong solutions of alkali metal Aisilicats with relatively .conc entrate'df mineral 4acids to produce a colloidalsolu'tion of silicicaCid. and

. the'same procedure is employedf for the'man'ufac- "tureof aluminagel and other'hydrousoxide gels "used as adsorberits.V `In all cases theconentra- Ations are such'thatthe entire reaction" mixture soonj sets'to ,a'hydrogeL and this'hydrogel is washed with hot water to'removejthe' free acid and mostof the waterf-fsolubl salts, Howeven it.

is impossible to reinoveth'augaii metal "sans from 'ahydrogel by this method to the extent necessaryjfor catalytic purposes, and therefore these tated silic'ic acidfgl by repeated filtration and silica and alumina-zirconium. oxide-silica cata- 1 washingl" This filas 'provento be avtedious and expensive procedure, for the'iiltration rate of aqueous suspensions of ordinary gelatinous silica isy extremely slow. "Moreoventhe alkallmetal ionsare adsorbed so 4'strongly vbythe continuous coating of gelatinous silica on afllter that large quantities of Wash Water are necessary for their removal, and the slow rate of penetration of the vvash 'Waterthrough alilter cloth coated with a layer of'gelatinous silica has increased still furyprocess is especially adapted to the large scale "f therthedifliculties encountered inA operating this process ona largev scale.

We havediscovered that an aqueous suspension of hydr'ou's oxides consisting oforcontainlng gel latinous'jhydrat'ed silica can be pretreated in such f a manner as to'iacilitate the filtration and washing' thereof without impairing vthe, activity of. gels 'v produced when the hydrated silica is dried and calcined. The most important feature of our'pretreatment is referred to hereinafter as a fiocculation step and the silica sc treated is referred to' as floccul'ated s i1ica,'but it should beunder- "stood that these terms referto the condition and 'behavio'r'of A' the silica or' .other hydrated metal 'oxide' duringjthe. dewatering'and Washing thereof amount ofnesnThe'present invention 1s rparwhich catalysts are substantially free from cornpounds ofalkali metals and are of relatively uniform particle size. A principal advantage of the invention resides in the factthatgel-type lcatalysts having these desirable properties can vbe preratlher than to any noticeable'ch'ange in the aqueous suspensionsafterthe 'occulating agent has been added. I lrlplacticing our invention wer subject"r the vaqueous suspensionsr containing' gelatinou's hydrated silica to a conditioning procedure which does not materially change the density. appearance or degree of dispersion rof the hydrated vsilica particlesin'the aqueous slurry, but

pared from such cheap and readily available -rnaterials as sodium and iwtassiurn silicates by the method thereof, which "method is especially adapted for large scale manufacture of cracking ,'which 'so modies these particles that they form a relatively thick', porousiiltercake'of good mechanical strength' instead ofthe 'ordinary thin,

slushy filter cakesthat are obtained when ordinary gelatinous silica suspensions are filtered. We believe that the water-dispersible adhesive colloids hereinafter referred to as fiocculating agents operate to modify in some way the electric charge on the hydrated silica particles in suspension, but the advantages f our invention are not limited by this theory of operation and the results obtained may be due partly or even wholly to other causes.

The flocculating agents which modify the gelatinous silica particles in the manner described point it may be stated that except where otherwise noted all the tanks subsequent to tank I are equipped with agitators which move very slowly, so that there is no tendency to break up or redisperse gels that have settled or been fiocculated. In the tank 3 sufficient additional acid is added to bring the pH to about 'LOZ-7.8 and are preferably added to the aqueous gelatinous silica suspension after the suspension has been aged for a period of time, although definite improvements are noted when the aging step has been omitted. We have found that aging appears to aid materially in obtaining a relatively thick and porous filter cake; in fact, we have noted some improvements in the filtration and washing of slurries of gelatinous hydrated silica which had been aged for 1-2 hours, but to which no occulating agentwas added. Our invention in its broader aspects therefore includes the combined steps of aging followed by filtration as one of its important features.

A number,` of important advantages are obtained by preconditioning pulps or slurries of gelatinous hydrated silica in the manner described above, prior to the dewatering thereof. We have found that inorganic salts such as sodium sulfate, sodium nitrate, sodium chloride and the like can be more rapidly and completely removed from a occulated silica slurry by washing as well as by filtration, and the silica can therefore be dewatered by any suitable procedure; Moreover, flocculation of the hydrated silica also resuits in a final dried product of much greater uniformity in partidle size, as compared with the irregular size of the particles obtained by drying hydro'gels of silica or silica and alumina obtained -by the ordinary methods heretofore employed.

Our invention in its broader aspects therefore includes the dewatering and washing of ilocculated silica by any suitable method including filtration, settling and decantation, thickening and the like.

The application of these discoveries to an improved method for the manufacture of gel-type catalysts suitable for use in hydrocarbon cracking and conversion reactions will be illustrated by the following description of a preferred method of catalyst manufacture with reference to the accompanying drawing. This drawing is a flow sheet in which the details of our preferred process are diagrammatically illustrated by tanks, Afilters and flow lines, but it should be understood that the invention in its broader aspects is not limited thereto.

In carrying out the process illustrated in the drawing wefirst prepare a dilute solution of sodium or potassium silicate in a mixing tank I, which is provided with a suitable high-speed im pellor-type or turbine type agitator 2 to obtain uniform mixing of the charge. The diluted water glass solution is neutralized with sulfuric, hydrochloric, nitric or other mineral acid to a pH of about 7.4-7.8, after which the agitation is con tinued for about 1/2 hour. The amounts and strength of the reagents are such that the solution contains about 5% S102.

After the preliminary acidification the contents of tank I are discharged into tank 3, which is a correction tank equipped with a suitable agitator and of a size suillcient to permit a retention of the charge for about '75 minutes. At this suflicient additional water to reduce the SiO: content to 3.8%.

After suitable retention in the correction tank 3 the gelatinous hydrated silica slurry resulting from the acid addition and dilution is passed to a blending and aging tank 4, wherein it may be aged under slow agitation for any suitable time. Aging of the slurry appears to increase the average particle size of the silica suspension either by agglomeration of the smaller particles or by their adhesion to larger sized particles. It will be noted that tanks 3 and 4 are both provided with side outlets, which permit the retention of about 25% of the aged suspension from a preceding batch to function as a nucleus for particle size growth.

The aged slurry is vpassed t0 tank 5, which is a flocculating apparatus in which the silica is fiocculated to a condition in which it is ready Afor filtering and washing to remove the water-soluble alkali metal salts. The slurry in tank 5 is first brought to a pH of 5-6 by the addition of suitable amounts of sulfuric acid or other mineral acid aftell which a flocculating agent is added. Representative adhesive colloids that we have used with success for this purpose are glue, gelatin, gluten and gluten-containing materials such as wheatv flour 'and the like. These and similar flocculating agents are preferably added as solutions or suspensions in water and are employed inv amounts of 0.001% to 0.1%. based on the weight of the slurry.

The flocculating agent is distributed uniformly throughout the hydrated silica suspension in tank ,5 by means of slow agitation, The resulting flocculated suspension is then pumped to the distrib- `utor box B, which is a wooden box of relatively large cross-sectional? area provided with one or more vertical partitions I and adapted to maintain the silica in a fiocculated condition while supplying a steady fiowof slurry to the filter Il. This may be an ordinary filter press or any other known type of filter, but is preferably a rotary -filter of the vacuum drum type provided with fine Water sprays for continuous washing of the filter cake, in order to aid in the separation of salts of alkali metals and other undesirable materialsfrom the silica.

. On the `filter 8 the silica can be Washed free from the major part of its Water-soluble impurities by wash water which may be acidified with a little sulfuric or hydrochloric acid, the filtration and washing being greatly aided by the flocculation of the silica in the tank 5. In large scale operation the wash water from this and other similar washing steps of the process is preferably 'panying salt solution and water as before. y In order to reduce still furtherthe content ofl from the repulper 9 may be passed Vthro'ughlline Il to a fiocculating and adjusting tank'IZ wherein the silica may be aged and flocculated by the addition of a flocculating agent if` desired." In

preparing mixed catalysts containing'the active silica together with other catalytically, active metal oxides and/or hydrogels the silica-slurry is rstpassed to one of the two tanks*I3,an`d,I4.- A

' lsuitable type, such as a-hotair or steam heated drier. By this means-we'may remove `rasfmuch as 40 to 60% ofthe water inthe filter cake, after which Lthe dryingof the partiallydried gel may.

be completediin a ycalcinerhof the rotary kiln type. Alternatively, the` drying maybe carried vout in one or more rotary' kilns, and such a calsolution ofaluminum sulfate or other salt of the 7 desired metal'is then added tothe slurry suspension after which sufficient ammonia is added as ammonium hydroxide to precipitate the hydratedmetal oxide from its salts. Thus, forexample,

' in the preparation o'f a silica-'aluminacatalyst of the type described in U. S. Patent No. 2,285,314 al solution of aluminum sulfate `in kwater 'is added to the slurry of silica in the tank I3 under continu-`rv ous agitation during one-halfhour after which 8%r aqua ammoniais added during 10-20 minutes to bring the'pI'li'to4.5-5.7.y In the preparation of modified catalysts a small amount of zirciner is illustrated on the drawing.

T hecalciner is preferably direct-'firedin a fire box 25 and sufficient capacity is provdedvto 'heat the catalyst to'temperatures of `1500o F. before it is discharged.' The dried' material is then ground in a. grinder 26 to io-mesh size and is obtained show the 'results obtained by the process of ourv conium or titanium sulfate may also be added and precipitated. By'employing thel tanks I3 and I4 in parallel it is possible, of course, tohandie a second batch of the semi-purified silica while the alumina or other polyvalent metal is being addedto and precipitated in the first batch, and any number of tanks may be employed in'thls vmanner in large scale operation.- y

After the addition and precipitation of alumina4 or other metal salts in`v the tanks I3 or Ilothe'resulting slurry is introduced intol the agingand occulation tank I5, Glue, gelatin or other` suitable flocculating agent may be added in approximately the rsame quantities that were used inthe the slurry much easier tollter. In the tankfl the slurry is preferably adjusted to L5-6% solids by the addition of water -if' necessary,"andv kept under slow .agitationuntil the hydrated alumina-silica mixture is ready for filtration and is a rotary filter similar to the'filter `8,- and the flocculated solids are separatedfrom the accomwashed with acidifled as a product containing not more'than0105% fNaz'O and little or n o FezOa'orother undesirable materials, v

The' following'specific examples are given to invention and also tovlllustrate the importance of certain features of .thisprocesa' remplie-ir Inpracticing the foregoing process. according .gto oneembodimentthereof, 4.36 tons ofsodium silicate in the form 4ofvv commercialwaterglass f `was added to .thevmix'ingtank I, together with Vtank 5 if desired, but'this'is 'not usually necessary since the hydrated aluminum oxide makesv 18.54 tons of water, and ,after completing the dilutionl 2.2 tons 'of `24.9% sulfuric acid were added. After agitatlng for one-half hour the 'resulting slurry was passedthrough the correctionand aging tanks 3 and"l,"as=previously described, and 0.015% of glue was added in the fiocculating tank 5l' After suitable floccul'ation ,the solids were then filteredioff on the filter 8 and washed with30.9 tons ofwatercontaining". sufficient sulfuric acid toreduce'the pH of 4the wash water to 2.8. The washed filter cake was repulped with 9.6 tons of water` in therepulper land run into tank I3, where a solution-*of 0.8

washing. It is thenpassed' to the -lter I6, which alkali metal salts, ammonium salts, and otherl undesirable water-soluble material from the silica-alumina mixture, the filter cake isagain' pref,-

erably reslurried in water-,in 'a second Vrepulper I'I and again filtered on la rotary filter I8, with or without reflocculation and aging in tank I9 depending on the condition of the solids .at this point. rIhe filter cake from 'the' filter I8 may then be reslurried once more in the repulper 20 .if desired, brought to a vsolids content of 5%.and

a pI-I of. 4.3-5.0 in the tank 2I kand filtered on the rotary filter 22 which is washed with water to remove the remaining water-Soluble impurities. The filter cake is then removed at approximately 10% solids onto a belt conveyor 23, which dis- In some cases, however, we havev lwas added.

ton of aluminum sulfatedin "1.16y tons of water y The alum Kwas' then precipitated by the addition of 1.87` tons of k8,%l\I IH4.OH solution and the resulting slurry wasr flocculated in vthe tank I5 by the addition oit-0.015%v ofglu'eas before., AAfter the following'filtrationstep the -cake on the'filter I6 was washed with 25.5 tons vof water containing sufficient sulfuric acid to reduce its pH to 2.5-3 and repulped in 12.9 tons The same quantities kof dilute lacid ofwater. V V and waterwere used ony the filter I8 and re- "Apulper 20, but 21.9`tons ofl'purewater were used to Wash the filter cake onj'the filter [22. YAfter 1 thei'calcination 1.26 tons of an oil-cracking catalyst were `obtained which contained 90% SiOz and"10% A1203 in a highly active condition'.

` Example 2f.

v52.5 pounds of water and 12.5pounds lof 41 B.- commercial` sodium silicate containing 28.5%

. ing. 6.5 pounds of 25% sulfuric acid were addedv SiO:y and 8.9% of NazO are run into a mixing tank f corresponding to the mixing tank I on the drawwlth the agitator 2 vat sufficiently high speed to keep the material moving away from the edges of the tankwhen the mixture became thick. After 30 minutes the resulting mixture was transferred to a tank corresponding to the flocculating tank 5 providedwith a slow-moving, v

gate-typeV agitator. v24 pounds ofv waterwere added along with 0.1-0.3 pounds-of 25% sulfurick acid .to reduce the pH to 6.8'7.8. The mixture was allowedto age for 2 hours, the pH was reduced to 5.5'by the addition of further quantities of sulfuric acid and a water-solution of glue was added equivalent to 0.015% of glue on the weight f y of the slurry. After completing the fiocculation o the hydrated silica the fioc was dewatered on a rotary filter such as an Oliver filter. vAbout 20 minutes were required for the filtration and the filter cake Was 0.75 inch thick. The filter cake was washed with water containing a small amount of hydrochloric acid by means of fine sprays at the rate of 2.5-3 gallons of water per pound of SiOz in the slurry. A sample of the filter cake was then found to contain about 0.2% of sodium on the weight of the SiOz.

Enough Water was added to the filter cake to make 70 pounds of slurry. To this slurry was added 2.3 pounds of aluminum sulfate containing 17% of A1203 in the form of 5` pounds of an aqueous solution. Ammonium hydroxide containing 15% of NH3 was then addedto bring the pH to 4.2-5.5. The mixture was ltered,

the filter. cake was washed as before andvslurried with enough Water to bring the solids content (SiOz plus A1203) to 4-6% and the mixture was again filtered and washed. This filter cake was again reslurried in water and filtered land the filter cake was washed and thoroughly dewatered. It was then found to contain NazO equivalent to only 0.01% of the weight of solids in the sample.

' Example 3 A gelatinous hydrated silica slurry was prepared exactly as described in Example 2, but was filtered Without the addition of glue. The filter cake was very wet and soft and fell away from the filter cloth when the Wash water .was applied. For this reason it was difficult to wash the filter cake on a filter of .the Oliver type.

Escdmple 4 720 parts by weight of 41 B. sodium silicate solution was dissolved in 2600 parts by weight `of water and the solution was placed in a kettle equipped with an agitator having three paddles which was rotated at 100 R. P. M. Acid was addedin 40 minutesto bring the pH to 3, after which the pH slowly rose to 5.0. It Was necessary to add sufficient acid to lower the pH to about 3 in order to neutralize the sodium in the grains of the hydrous SiOz, since these grains vary in size from a .few microns to 1/8" in diame- 8 but a .three hour period was necessary to filter the resulting suspension and only a small amount of wash water could be passed through the filter cake.

VExample 5 12.5 lbs. of 41 B. sodium silicate containing 8.5% of 'NazO and 28.5% of SiOz was diluted with 52.5 lbs. of pure water lin a mixer of the turbine type (see Chemical Engineering Handbook, p. 1288). 6.5 lbs. of 25% sulfuric acid were added with vigorous agitation .during 20-30 minutes, afterlwhich the mixer was emptied and Washed with 24 lbs. of Water containing 0.3-0.4 lb. of 25% sulfuric acid. The Wash water was added to the precipitated silica slurry and the mixture was aged for 1.5-2 hours at a pH of 7.0-7.3. A

A Water solution of glue was then added in amounts of (ml-0.02% of glue and the flocculated hydrous silica was dewatered by filtration. A dried sample of the filter cake contained 0.22% sodium.

The filter cake was washed on the filter with an amount of wash water equal to the original weight of the slurry, sludged up with a little water and aged for 12 hours. It was then diluted with water to 4-6% solids, 5% being the preferred figure, 0.015% of glue was again added. and the silica slurry was again filtered and the filter cake washed with acidified water. The sodium con tent of a dried sample of the filter cake was 0.02%. The aging, fiocculation,A filtration and washing was repeated a third time,rbut in this case no acid was used inl the Wash Water. This reduced the sodium content to 0.01%. The filter cake was then calcined as described in Example l and the resulting pure *silica catalyst Was ground to 4-6 mesh.` It was well suited for use as a dehydration catalystvfor the production of butadiene from butylene glycols.

What we claim is:

1. A method of preparing a silica-containing catalyst which comprises the steps of neutralizing ank aqueous alkali metal silicate solution by the addition of an vacid to form an aqueous slurry of gelatinous'silica containing alkali metal salts, aging the slurry, adding glue to flocculate the silica, and separating the alkali metal salts by dewatering and washing.

2. A method of preparing a silica-containing catalyst which comprises the steps of neutralizing an aqueous alkali metal silicate solution by the Aaddition of an acid to.form an aqueous slurry of gelatinous silicaV containing alkali metal salts, aging the slurry, adding glue to flocculate the silica, and. separating the alkali metal salts by filtering off the fiocculated silica and washing the lter cake.

KENNETH D. ASHLEY. ALPHONS O. JAEGER. 

